CN1288161C - Linked metallocene complexes, catalyst systems, and olefin polymerization processes - Google Patents

Linked metallocene complexes, catalyst systems, and olefin polymerization processes Download PDF

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Publication number
CN1288161C
CN1288161C CNB028208803A CN02820880A CN1288161C CN 1288161 C CN1288161 C CN 1288161C CN B028208803 A CNB028208803 A CN B028208803A CN 02820880 A CN02820880 A CN 02820880A CN 1288161 C CN1288161 C CN 1288161C
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cyclopentadiene
metallocene
group
alkyl
bridged
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CN1575295A (en
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M·W·赫尔特卡普
L·G·麦克古劳戈
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Univation Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

Disclosed are metallocene complexes containing two or more metallocene components where the components may be independently bridged or unbridged. In particular, the invention provides metallocene complexes including a bridged metallocene component linked to an unbridged metallocene component where a ligand structure of the unbridged metallocene component is linked to the bridging group of the bridged metallocene component. The invention provides metallocene complexes including a first unbridged metallocene component linked to second unbridged metallocene component via their ligand structures. The invention also provides metallocene complexes including a bridged metallocene component linked to a second bridged metallocene component via their ligand structures. The invention further provides methods of preparing the linked metallocene complexes described above, catalyst systems including these linked metallocene complexes, polymerization processes utilizing these complexes, and polymers made thereby.

Description

Connect metallocene complex, the olefine polymerizing process of catalyst system and this catalyst system of use
The field of the invention
The present invention relates to the polymerizing catalyst title complex, comprise the catalyst system of these catalyst complexes, and they are used for the purposes of olefinic polymerization.Especially, the present invention relates to metallocene complex, it comprises two or more metallocene components that link together.Specifically, these metallocene components link together by the ligand structure of at least one metallocenes.The invention still further relates to the catalyst system and their purposes in olefine polymerizing process that contain these metallocene complexes.
Background of the present invention
The metallocene-type catalyst system is used for obtaining being used for the various new polymerss of various application and product in polymerization process purposes is well-known in the art.The polymkeric substance that is obtained by metalloscene catalyst has excellent performance such as the physical strength and the transparency.Yet these polymkeric substance more are difficult to processing usually.
In order to obtain to have the polymeric articles of improvement physicals and the polymkeric substance of easier processing, the industrial concentrated physical blending of studying two or more polymkeric substance is placed hope on the optimal performance that this blend polymer shows its component polymer.Other then is conceived to use two or more reactors to produce blend on the spot or be conceived to use two or more catalyzer to produce required polymer product in reactor.
Yet, can not be by the polymkeric substance of those characteristics predictions of the polymkeric substance that uses each catalyzer to produce separately if utilize two kinds of different catalyzer generally to obtain its characteristic.This unpredictability is for example caused by the competition between employed catalyzer or catalyst system or other influence.In addition, these polymkeric substance generally do not have the preferred equilibrium of workability and strength property.Therefore, exist demand for the metallocene catalyst system of the processable polymer that can produce desirable combination in the art with processing, machinery and optical property.
U.S. patent No.5,830,958 disclose by the substituent metallocenes that allows one of group of wherein containing cyclopentadienyl have to contain olefinic or acetylene series unsaturated link(age) and have reacted the method for preparing multinuclear metallocena with having from the metal of VIb-Vib family and second metallocenes of metal-hydrogen negative ion key.
U.S. patent No.6,153,776 disclose 3-6 family or the lanthanide complex with two metal centers, by with this title complex and strong lewis acid, the Bronsted hydrochlorate contains the salt binding of cation oxidant or carries out bulk electrolysis (bulk electrolysis) and the catalyzer of acquisition in the presence of the non-coordination anion of consistency inertia.
U.S. patent No.6,262,197 disclose and have contained at least two metallocenes fragment L-MX 2The Metallocenic compound of-L.
EP 0 953 581 A1 disclose has the R of being connected in IOSiR II 3The carrying metal of the part of group is luxuriant, wherein R IBe to contain 1-20 carbon atom and optional heteroatomic divalent aliphatic alkyl or the SiR of containing II 2Group, and R IIBe C 1-20Alkyl, C 3-20Cycloalkyl, C 6-20Aryl, C 3-20Alkenyl, C 7-20Aralkyl, C 8-20Aromatic yl alkenyl, or C 7-20Alkaryl linearity or branching group.
People such as Spalek are at " the novel bridging zirconocene that is used for olefinic polymerization: double-core and hybrid structure ", disclose among Journal of Molecular Catalysis A:Chemical 128 (1998) 279-287 to be used for liquid propene polymeric bridged bis-indenyl zirconocene.
General introduction of the present invention
In one aspect, the invention provides the metallocene complex that is connected of at least one bridged metallocene component with interconnection and at least one non-bridged metallocene components, wherein the ligand structure of non-bridged metallocene components is connected in the bridged group of bridged metallocene component.
In yet another aspect, the invention provides wherein, the first bridged metallocene component is connected in non-bridged metallocene components, and this non-bridged metallocene components is connected in the connection metallocene complex of the second bridged metallocene component, wherein first ligand structure of non-bridged metallocene components is connected in the bridged group of the first bridged metallocene component, and second ligand structure of this non-bridged metallocene components is connected in the bridged group of this second bridged metallocene component.
In yet another aspect, the invention provides the metallocene complex that is connected of the first non-bridged metallocene components with interconnection and the second non-bridged metallocene components, wherein the ligand structure of the first non-bridged metallocene components is connected in the ligand structure of the second non-bridged metallocene components.
In yet another aspect, the invention provides the first non-bridged metallocene components and be connected in the second non-bridged metallocene components, and this second non-bridged metallocene components is connected in the connection metallocene complex of the 3rd non-bridged metallocene components, wherein the ligand structure of the first non-bridged metallocene components be connected in first ligand structure of the second non-bridged metallocene components and wherein second ligand structure of the second non-bridged metallocene components be connected in the ligand structure of the 3rd non-bridged metallocene components.
Aspect another, the invention provides the first bridged metallocene component and be connected in non-bridged metallocene components, and this non-bridged metallocene components is connected in the connection metallocene complex of the second bridged metallocene component, wherein the ligand structure of first bridged metallocene be connected in first ligand structure of this non-bridged metallocenes and wherein the ligand structure of second bridged metallocene be connected in second ligand structure of this non-bridged metallocene components.
More specifically, the invention provides a kind of metallocene complex, comprising:
(a) contain at least a bridged metallocene component of first bridged group; With
(b) have the non-bridged metallocene components of first aromatic ring system and second aromatic ring system, wherein first aromatic ring system of non-bridged metallocenes is connected in first bridged group; With
(c) contain the second bridged metallocene component of second bridged group, wherein second aromatic ring system of non-bridged metallocenes is connected in second bridged group.
The present invention also provides the method for preparing above-mentioned connection metallocene complex, comprises that these connect the catalyst system of metallocene complex, utilizes the polymerization process of these title complexs, and the polymkeric substance for preparing thus.
Describe in detail
Have been found that the novel catalyst system that comprises the metallocenes that connects on the structure, and prepared the route of synthesis that these connect metallocenes.Preferably, this connection metallocenes comprises the two or more metallocenes structures by the part skeleton connection of at least one metallocenes structure.
For patent specification, term " catalyzer " is meant metallic compound, when it combines with activator, makes olefinic polymerization.Term " activator " can exchange use with term " promotor ", and " catalyst system " is meant the binding substances of catalyzer, activator and optional solid support material.
Connection metallocene complex of the present invention
In one embodiment, connect metallocene complex and contain interconnected at least one bridged metallocene component and at least one non-bridged metallocene components, wherein the ligand structure of non-bridged metallocene components is connected in the bridged group of bridged metallocene component.In this embodiment, two ligand structures connect together by connecting base.
In another embodiment, connecting metallocene complex represents with general formula I:
General formula I
In general formula I, each M independently is the atoms metal of the periodic table of elements, can be 3-12 family metal or group of the lanthanides or actinide metals, preferred each M independently is the 3-10 group 4 transition metal, more preferably each M independently is 4,5 or 6 group 4 transition metals, even more preferably each M independently is zirconium, hafnium or titanium.Most preferably each M is a zirconium.
In general formula I, each Q represents to be bonded in the leavings group of each M.For patent specification and appended claims, term " leavings group " can be captured on metallocene catalyst compound, thereby forms the cationic any part of metalloscene catalyst that can make one or more olefinic polymerizations.Each Q independently is a single anion ligand, or two group Q form the dianion chelating ligand together.In one embodiment, Q is the unstable part of single anion with the σ key that is connected in M.In preferred embodiments, two single anion leavings group Q are bonded in each M.
In one embodiment, each Q independently is a halogen, and alkyl has the alkyl of 1-20 carbon atom, hydride ion, carboxylate radical, diene, ether, amide, or phosphide.Preferably, each Q independently is selected from halogen, C 1-C 6Alkyl, C 6-C 10Aryl, C 7-C 12Aralkyl and C 7-C 12Alkaryl.
In general formula I, each n independently is 0,1 or 2, depends on the oxidation state of metal, makes that above general formula (I) is a neutral compound.In preferred embodiments, each n is 2.
In general formula I, L A, L BBe bonded in first atoms metal M, and L CAnd L DBe bonded in second atoms metal M.L A, L B, L CAnd L DBe aromatic ring system, they can be identical or different, generally are made up of the atom that is selected from the periodic table of elements 13-16 family.Preferably, these atoms are selected from carbon, nitrogen, oxygen, silicon, sulphur, phosphorus, germanium, boron, aluminium and their combination.Most preferably, this aromatic ring or member ring systems are cyclopentadienyl and class cyclopentadienyl (cyclopentadienyl-type) parts that does not replace or replace, wherein " class cyclopentadienyl ligands " is meant and contains cyclopentadienyl, or dependency structure, for example wherein one or more carbon of cyclopentadienyl ligands by the part of one or more heteroatomss such as N, O and S metathetical structure.Their non-limitative example comprises the cyclopentadienyl that does not replace and replace, indenyl, benzo indenyl, fluorenyl, the camomile cyclic group, pyrryl, pyrazolyl, the assorted benzene part of carbazyl and boron etc., the hydrogenation modification that comprises them, for example tetrahydro indenyl, tetrahydrofluorenyl and octahydrofluorenyl part.
In one embodiment, L A, L B, L CAnd L DIndependently be selected from cyclopentadienyl separately, indenyl, fluorenyl and benzindene ylidene ligands and their partial hydrogenation form, for example tetrahydro indenyl.Also have, these member ring systems can be not replace or be substituted as described below.
In another embodiment, L A, L B, L CAnd L DOptional and/or independence is replaced by one or more substituting groups.Substituent limiting examples is linearity, branching and cyclic alkyl, alkenyl and alkynyl, aryl; aralkyl and alkaryl, acyl group, aroyl; alkoxyl group, aryloxy, alkylthio; dialkyl amido, alkoxy carbonyl, aryloxycarbonyl; formamyl, alkyl and dialkyl amido formyl radical, acyloxy; acyl amino, aroylamino and their combination.In one embodiment, if any, substituting group has 50 non-hydrogen atoms at the most, 1-30 carbon atom for example, more preferably 1-20 carbon atom, also more preferably 1-12 carbon atom.And these substituting groups can also for example be fluoridized and/or chlorination by halogenation.
L A, L B, L CAnd L DOptional substituent example and non-limitative example comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, tolyl and xylyl etc. comprise all their isomer, the tertiary butyl for example, sec.-propyl etc.In addition, other feasible substituent non-limitative example comprises the organic quasi-metal group that alkyl replaces, trimethyl silyl for example, trimethylammonium germyl and methyl diethylsilane base etc.; And the organic quasi-metal group of brine alkyl (halocarbyl) replacement, comprise three (trifluoromethyl) silyl, methyl-two (difluoromethyl) silyl and brooethyl dimethyl germyl etc.; With dibasic borine group, comprise dimethyl boryl etc.; With two replacement pnicogen groups, comprise dimethylamino, dimethyl phosphino-, diphenyl amino, aminomethyl phenyl phosphino-etc.; With the chalcogen group, comprise methoxyl group, oxyethyl group, propoxy-, phenoxy group, methylthio group and ethylmercapto group etc.Generally, substituent non-hydrogen atom is selected from carbon, silicon, boron, aluminium, nitrogen, phosphorus, oxygen, tin, sulphur, germanium and halogen.Also have, at least two substituting groups, preferred two adjacent substituting groups can connect into has the ring structure that is selected from 3-30 atom in carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or their combination.
In another embodiment, L A, L B, L CAnd L DIndependently be selected from separately and replace or unsubstituted cyclopentadienyl indenyl, fluorenyl and benzindene ylidene ligands, and their partial hydrogenation form, for example tetrahydro indenyl.In another embodiment, Ren Xuan substituting group is selected from the alkyl with 1-4 carbon atom.
In general formula I, A connects L AAnd L BBridged group.A also is connected in L by R CIn one embodiment, bridged group A contains at least one 13-16 family atom, usually is referred to as the divalence structure division, for example but be not limited at least one or their combination in carbon, oxygen, nitrogen, silicon, aluminium, boron, germanium and the tin atom.Preferably, bridged group A contains carbon, silicon or germanium atom, and most preferably A contains at least one Siliciumatom or at least one carbon atom.In another embodiment, A can also be the 13-16 family atom that contains more than 2 or 2, the long bridged group of preferred 13-16 family atom more than 3 or 3.Bridged group A can also contain the substituting group just like above definition, comprises halogen.In another embodiment, bridged group A RC ', R ' Si, R ' SiR ' Si, R ' Ge, P, or R ' 2Si-O-R ' 2Si represents that wherein R ' belongs to hydride ion group, alkyl, substituted hydrocarbon radical, brine alkyl replaces brine alkyl, the organic quasi-metal that alkyl replaces, the organic quasi-metal that brine alkyl replaces, two replace boron, and two replace pnicogen, replace chalcogen, or the group of halogen, perhaps two or more R ' can connect into ring or member ring systems.
In general formula I, R connects A and L CThe connection base.In one embodiment, connecting basic R is as the following defined 1-100 of having, 000 carbon atom, 1-10,000 carbon atom, 1-1000 carbon atom, 1-500 carbon atom, 1-100 carbon atom, 1-20 carbon atom, 1-10 carbon atom, or the replacement of 1-6 carbon atom or unsubstituting hydrocarbyl.In another embodiment, connecting basic R is to contain 3 above carbon atoms, preferred more than 6, more than 20, or the replacement of the carbon atom more than 100 or unsubstituting hydrocarbyl.In another embodiment, connecting basic R is to contain 3 above carbon atoms, preferred more than 6, more than 20, or the replacement of 100 above carbon atoms or unsubstituting hydrocarbyl.In another embodiment, connecting basic R replaces or not substituted alkyl, alkenyl, alkoxyl group or aryl as defined below.In another embodiment, R has 1-100,000 carbon atom, 1-1000 carbon atom, 1-500 carbon atom, 1-100 carbon atom, 1-20 carbon atom, 1-10 carbon atom, or the replacement of 1-6 carbon atom or substituted alkyl not.In another embodiment, connect basic R and contain at least one heteroatoms that is selected from 13-16 family, can also comprise heterocyclic group.Preferably, this at least one heteroatoms is selected from N, P, O and S or their any subclass.
In another embodiment, the connection metallocene complex of general formula I comprises that belonging to good comonomer introduces the first bridged metallocene component of metallocenes structure and belong to the second non-bridged metallocene components that bad comonomer is introduced thing.For this specification sheets and claims, bad comonomer is introduced thing and is defined as having introduced and is lower than the 6mol% comonomer, preferably be lower than the 4mol% comonomer, metallocene catalyst components more preferably less than the 2mol% comonomer, and good comonomer introducing thing is a metallocene catalyst components of having introduced more comonomers, introduces thing with bad comonomer and compares.
In another embodiment, the connection metallocene complex of general formula I for example can prepare by cyclopentadiene or the class cyclopentadiene part that formation has a halogenated alkyl structure division.This by allow replace or unsubstituted ring pentadiene or class cyclopentadiene compound (K) salt such as lithium methide or n-Butyl Lithium, are finished thereby form corresponding cyclopentadiene lithium as reacting in the tetrahydrofuran (THF) at suitable solvent for Li, Na with basic metal.The cyclopentadiene lithium then with general formula X-R-A-X 2The compound reaction of R, wherein X is a halogen, preferred X is a chlorine; Each R is independent as defined above; A as defined above, preferred A is silicon or germanium atom, more preferably A is a Siliciumatom.
Can react with second cyclopentadiene or class cyclopentadiene structure (Cp2) lithium with the above product of X-R-AX-Cp1 (wherein Cp1 represents first cyclopentadiene or class cyclopentadiene structure) expression, this Cp2 can be identical or different with Cp1, obtained X-R-ACp2Cp1.
More than product X-the R-ACp2Cp1 of Huo Deing then with the amination metal reaction, obtain to contain the amination metallocenes of reactive halogenated alkyl structure division.For example, X-R-ACp2Cp1 with have a formula M (NR 2) 4The amination melts combine, wherein for the present embodiment, M is an atoms metal, preferred 4 family's metals, preferred Zr or Hf and more preferably Zr, and R is the alkyl with 1-6 carbon atom.Amino ligands used herein is as blocking group, so that keep the structure identity of metallocenes group in the structure of follow-up metallocene components or connection procedure.For example ,-the NR2 part prevents that metal from carrying out undesirable reaction such as butylation or reduction.These blocking groups are as described below can be replaced afterwards.
More than the product of Huo Deing reacts with the 3rd cyclopentadiene or class cyclopentadiene structure (Cp3) lithium then, and this Cp3 can be identical or different with Cp1 and/or Cp2, obtained (Cp2) M (NR of H-Cp3-R-A (Cp1) 2) 2, for example can use the butyllithium deprotonation then, form (Cp2) M (NR of Li-Cp3-R-A (Cp1) 2) 2
Li-Cp3-R-A (Cp1) is M (NR (Cp2) 2) 2With Cp4MCl 3Reaction obtained Cp4MCl 2-Cp3-R-A (Cp1) is M (NR (Cp2) 2) 2, wherein Cp4 the 4th replaces or unsubstituted cyclopentadiene or class cyclopentadiene structure, and it can be identical or different with Cp1 and/or Cp2 and/or Cp3.
Cp4MCl 2-Cp3-R-A (Cp1) is M (NR (Cp2) 2) 2For example can react then, obtain Cp4MCl with the excess chlorine trimethyl silane 2-Cp3-R-A (Cp1) is MCl (Cp2) 2
In one embodiment, connect metallocene complex and contain the first bridged metallocene component, non-bridged metallocene components and the second non-bridged metallocene components that connects successively.In this embodiment, first ligand structure of non-bridged metallocene components is connected in the bridged group of the first bridged metallocene component, and second ligand structure of non-bridged metallocene components is connected in the bridged group of the second bridged metallocene component.
In another embodiment, connecting metallocene complex represents with general formula I I.
General formula I I
In general formula I I, atoms metal M, leavings group Q, n, ligand L A, L B, L CAnd L D, bridged group A be connected basic R such as above in general formula I definition.L EAnd L FIndependently as the L that in general formula I, defines A, L B, L CAnd L DDefine like that.B is a bridged group, and is identical with the A definition in general formula I.B can be identical or different with A.
In one embodiment, in general formula I I, L A, L B, L C, L D, L EAnd L FEach replaces or unsubstituted cyclopentadienyl naturally, indenyl, fluorenyl and benzindene ylidene ligands and their partial hydrogenation form, for example tetrahydro indenyl.In addition, in another embodiment, L AWith L EIdentical, L BWith L FIdentical, L CWith L DIdentical, and be connected in L AAnd L BMetal be connected in L EAnd L FAtoms metal identical.In another embodiment, Ren Xuan substituting group is selected from the alkyl with 1-4 carbon atom.
In another embodiment, the connection metallocene complex of general formula I I comprises the first and second bridged metallocene components that belong to good comonomer introducing metallocenes, and introduces thing with this good comonomer and compare the non-bridged metallocene components that belongs to bad comonomer introducing thing.
In another embodiment, the connection metallocene complex of general formula I I for example can prepare by cyclopentadiene or the class cyclopentadiene part that formation has a halogenated alkyl structure division.This by allow replace or unsubstituted ring pentadiene or class cyclopentadiene compound (K) salt such as lithium methide or n-Butyl Lithium, are finished thereby form corresponding cyclopentadiene lithium as reacting in the tetrahydrofuran (THF) at suitable solvent for Li, Na with basic metal.The cyclopentadiene lithium then with general formula X-R-A-X 2The compound reaction of R, wherein X is a halogen, preferred X is a chlorine; Each R is independent as defined above; A as defined above, preferred A is silicon or germanium atom, more preferably A is a Siliciumatom.
Can react with second cyclopentadiene or class cyclopentadiene structure (Cp2) lithium with the above product of X-R-AX-Cp1 (wherein Cp1 represents first cyclopentadiene or class cyclopentadiene structure) expression, this Cp2 can be identical or different with Cp1, obtained X-R-ACp2Cp1.
More than product X-the R-ACp2Cp1 of Huo Deing then with the amination metal, preferred 4 families amination metal reaction obtains to contain the amination metallocenes of reactive halogenated alkyl structure division.For example, X-R-ACp2Cp1 with have a formula M (NR 2) 4The amination melts combine, wherein for the present embodiment, M is 4 family's metals, preferred Zr or Hf and more preferably Zr, and R is the alkyl with 1-6 carbon atom.
More than the product of Huo Deing reacts with the 3rd cyclopentadiene or class cyclopentadiene lithium structure (Cp3) then, and this Cp3 can be identical or different with Cp1 and/or Cp2, obtained (Cp2) M (NR of H-Cp3-R-A (Cp1) 2) 2, for example can use the butyllithium deprotonation then, form (Cp2) Zr (NR of Li-Cp3-R-A (Cp1) 2) 2
Two normal product Li-Cp3-R-A (Cp1) are Zr (NR (Cp2) 2) 2With MCl 4Reaction has obtained Cl 2M[Cp3-R-A (Cp1) is Zr (NMe (Cp2) 2) 2] 2
Cl 2M[Cp3-R-A (Cp1) is Zr (NMe (Cp2) 2) 2] 2With the reaction of excess chlorine trimethyl silane, obtain Cl then 2Zr[Cp3-R-A (Cp1) is ZrCl (Cp2) 2] 2
In one embodiment, connect metallocene complex and contain the interconnected first non-bridged metallocene components and the second non-bridged metallocene components, wherein the ligand structure of the first non-bridged metallocene components is connected in the ligand structure of the second non-bridged metallocene components.
In another embodiment, connecting metallocene complex represents with general formula III.
Figure C0282088000131
General formula III
In general formula III, atoms metal M, leavings group Q, n, ligand L A, L B, L C, L DBe connected basic R such as above in general formula I definition.
In another embodiment, the connection metallocene complex of general formula III comprises the metallocene components that the good comonomer that belongs to is as defined above introduced the metallocene components of metallocenes structure and belonged to the bad comonomer introducing thing of comparing with the former.For example, the Hf analogs is known is to introduce thing than the better comonomer of their Zr homologue.
In another embodiment, the connection metallocene complex of general formula III for example can prepare by cyclopentadiene or the class cyclopentadiene part that formation has a halogenated alkyl structure division.This by allow replace or unsubstituted ring pentadiene or class cyclopentadiene compound (K) salt such as lithium methide or n-Butyl Lithium, are finished thereby form corresponding cyclopentadiene lithium as reacting in the tetrahydrofuran (THF) at suitable solvent for Li, Na with basic metal.The cyclopentadiene lithium then with the reaction of the compound of general formula Cl-R-Br, wherein each R is independent as defined above; A as defined above, preferred A is silicon or germanium atom, more preferably A is a Siliciumatom.
(wherein Cp1 represents first cyclopentadiene or class cyclopentadiene structure to product X-R-Cp1, X is a halogen, with R as defined above) then with the amination metal, preferred 4 families amination metal reaction obtains to contain the amination metallocenes of reactive halogenated alkyl structure division.Cl-R-Cp1 with have a formula M (NR 2) 4The amination melts combine, wherein for the present embodiment, M is 4 family's metals, preferred Zr or Hf and more preferably Zr, and R is the alkyl with 1-6 carbon atom.
Above Fan Ying product (Cl-R-Cp1) M (NR 2) 3With the reaction of chlorine trimethyl silane, obtain (Cl-R-Cp1) M (NR then 2) 2Cl.
Above product and 2 normal cyclopentadiene or the reaction of class cyclopentadiene structure lithium obtain (HCp2-R-Cp1) Cp2M (NR 2) 2, wherein Cp2 represents second cyclopentadiene or class cyclopentadiene structure, it can be identical or different with Cp1.
Product (HCp2-R-Cp1) Cp2M (NR 2) 2For example can react then, form (LiCp2-R-Cp1) Cp2M (NR with butyllithium 2) 2, the latter can be further and Cp3MCl 3Reaction, wherein Cp3 represents the 3rd cyclopentadiene or class cyclopentadiene structure, it can be identical or different with Cp1 and/or Cp2, obtained (Cl 2MCp3Cp2-R-Cp1) Cp2M (NR 2) 2
Above reaction product can be reacted with the chlorine trimethyl silane then, obtains product (Cl 2MCp3Cp2-R-Cp1) Cp2MCl 2
In one embodiment, connect metallocene complex and contain the first non-bridged metallocene components, the second non-bridged metallocene components and the 3rd non-bridged metallocene components that connects successively, wherein the ligand structure of the first non-bridged metallocene components is connected in the ligand structure of the second non-bridged metallocene components, and wherein the ligand structure of the second non-bridged metallocene components is connected in the ligand structure of the 3rd non-bridged metallocene components.In another embodiment, connecting metallocene complex represents with general formula I V.
Figure C0282088000151
General formula I V
In general formula I V, atoms metal M, leavings group Q, n, L A, L B, L C, L D, L E, L FWith to be connected basic R identical with the definition in general formula I and II.
In another embodiment, the connection metallocene complex of general formula I V comprises that belonging to good comonomer introduces the metallocene components of thing and belong to those components that bad comonomer is introduced thing.
In one embodiment, in general formula I V, L A, L B, L C, L D, L EAnd L FEach replaces or unsubstituted cyclopentadienyl naturally, indenyl, fluorenyl and benzindene ylidene ligands, and their partial hydrogenation form, for example tetrahydro indenyl.In addition, in another embodiment, L AWith L FIdentical, L BWith L EIdentical, L CWith L DIdentical, and be connected in L AAnd L BAtoms metal be connected in L EAnd L FAtoms metal identical.In another embodiment, Ren Xuan substituting group is selected from the alkyl with 1-4 carbon atom.
In another embodiment, the connection metallocene complex of general formula I V for example can prepare by cyclopentadiene or the class cyclopentadiene part that formation has a halogenated alkyl structure division.This by allow replace or unsubstituted ring pentadiene or class cyclopentadiene compound (K) salt such as lithium methide or n-Butyl Lithium, are finished thereby form corresponding cyclopentadiene lithium as reacting in the tetrahydrofuran (THF) at suitable solvent for Li, Na with basic metal.The cyclopentadiene lithium then with the reaction of the compound of general formula Cl-R-Br, wherein R is as defined above.Preferably, R is the alkyl that defines in general formula I as above.
Product C l-R-Cp1 then with 4 families amination metal reaction, obtain to contain the amination metallocenes of reactive halogenated alkyl structure division.Cl-R-Cp1 with have a formula M (NR 2) 4The amination melts combine, wherein for the present embodiment, M is 4 family's metals, preferred Zr or Hf and more preferably Zr, and R is the alkyl with 1-6 carbon atom, thereby formation (X-R-Cp1) 2M (NR 2) 2
Above Fan Ying (X-R-Cp1) 2M (NR 2) 2Product reacts with cyclopentadiene or class cyclopentadiene structure lithium then, obtains (H-Cp2-R-Cp1) 2M (NR 2) 2, wherein Cp2 represents second cyclopentadiene or class cyclopentadiene structure, it can be identical or different with Cp1.The product of this reaction can be used the butyllithium deprotonation then, forms (Li-Cp2-R-Cp1) 2M (NR 2) 2
Product (Li-Cp2-R-Cp1) 2M (NR 2) 2With Cp3MCl 3Reaction obtains (Cp3MCl 2-Cp2-R-Cp1) 2M (NMe 2) 2, wherein Cp3 is the 3rd cyclopentadiene or class cyclopentadiene structure, it can be identical or different with Cp1 and/or Cp2.
(Cp3MCl 2-Cp2-R-Cp1) 2M (NR 2) 2For example can react then, obtain product (Cp3MCl with the excess chlorine trimethyl silane 2Cp2-R-Cp1) 2MCl 2
In one embodiment, connect the first bridged metallocene component, non-bridged metallocene components and the second bridged metallocene component that metallocene complex contains interconnection successively, wherein the ligand structure of first bridged metallocene be connected in first ligand structure of non-bridged metallocenes and wherein the ligand structure of second bridged metallocene be connected in second ligand structure of non-bridged metallocene components.In this embodiment, connecting metallocene complex represents with general formula V.
Figure C0282088000161
General formula V
In general formula V, atoms metal M, leavings group Q, n, ligand L A, L B, L C, L D, L E, L F, bridged group A and B, and it is identical with the definition in general formula I and II to connect basic R.
In one embodiment, in general formula I I, L A, L B, L C, L D, L EAnd L FEach replaces or unsubstituted cyclopentadienyl naturally, indenyl, fluorenyl and benzindene ylidene ligands, and their partial hydrogenation form, for example tetrahydro indenyl.In addition, in another embodiment, L AWith L FIdentical, L BWith L EIdentical, L CWith L DIdentical, and be connected in L AAnd L BAtoms metal be connected in L EAnd L FAtoms metal identical.In another embodiment, Ren Xuan substituting group is selected from the alkyl with 1-4 carbon atom.
In another embodiment, the connection metallocene complex of general formula I I comprises that belonging to good comonomer introduces the first and second bridged metallocene components of metallocenes structure and belong to the non-bridged metallocene components that bad comonomer is introduced thing.
In another embodiment, the connection metallocene complex of general formula V for example can prepare by cyclopentadiene or the class cyclopentadiene part that formation has a halogenated alkyl structure division.This by allow replace or unsubstituted ring pentadiene or class cyclopentadiene compound (K) salt such as lithium methide or n-Butyl Lithium, are finished thereby form corresponding cyclopentadiene lithium as reacting in the tetrahydrofuran (THF) at suitable solvent for Li, Na with basic metal.The cyclopentadiene lithium then with the reaction of the compound of general formula Cl-R-Br, wherein each R is independent as defined above; A as defined above, preferred A is silicon or germanium atom, more preferably A is a Siliciumatom.
More than product X-the R-Cp1 of Huo Deing then with the amination metal, preferred 4 families amination metal reaction obtains to contain the amination metallocenes of reactive halogenated alkyl structure division.Cp1 is cyclopentadiene or class cyclopentadiene structure.X-R-Cp1 with have a formula M (NR 2) 4The amination melts combine, wherein for the present embodiment, M is 4 family's metals, preferred Zr or Hf and more preferably Zr, and R is the alkyl with 1-6 carbon atom.
More than Fan Ying product and cyclopentadiene or class cyclopentadiene structure lithium reaction obtains (H-Cp2-R-Cp1) 2M (NR 2) 2, the latter can use the butyllithium deprotonation then, forms (Li-Cp2-R-Cp1) 2M (NR 2) 2Cp2 is cyclopentadiene or class cyclopentadiene structure, and it can be identical or different with Cp1.
Product (Li-Cp2-R-Cp1) 2M (NR 2) 2With X 2The A reaction obtains (X-A-HCp2-R-Cp1) 2M (NR 2) 2, it can further react with cyclopentadiene or class cyclopentadiene structure lithium, obtains (HCp3-A-HCp2-R-Cp1) 2M (NR 2) 2, wherein Cp3 is cyclopentadiene or class cyclopentadiene structure, it can be identical or different with Cp1 and/or Cp2.
(HCp3-A-HCp2-R-Cp1) 2M (NR 2) 2Can with M (NR 2) 4Reaction obtains ((R 2N) 2MCp3-A-Cp2-R-Cp1) 2M (NR 2) 2, the latter can further react with the chlorine trimethyl silane, obtains product (Cl 2MCp3-A-Cp2-R-Cp1) 2MCl 2
In above general formula I-V, in preferred embodiments, M is metal and the periodic table of elements group of the lanthanides that is selected from 3-10 family, preferred 3-6 family, the more preferably metal among 4 family's metals such as Zr and the Hf; If present, ligand L A, L B, L C, L D, L EAnd L FIndependently be selected from replacement or unsubstituted ring pentadienyl part and class cyclopentadienyl ligands, preferably do not replace or substituted cyclopentadienyl indenyl or fluorenyl ligand; A and/or B comprise carbon, silicon, or germanium; R replaces or substituted alkyl not, alkenyl, and alkoxyl group or aryl, each Q independently is selected from halogen and alkyl, or two group Q form the dianion chelating ligand together; With n be 0,1 or 2, depend on the form oxidation state of M.
Term used herein " alkyl " is meant straight chain, side chain or cyclic alkyl.The example of these groups is including, but not limited to methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, hexyl, 2-ethylhexyl, octyl group, cyclopentyl, cyclohexyl etc.Cycloalkyl can be replaced (promptly can be alkyl-cycloalkyl, as methylcyclohexyl etc.) by one or more straight chains and/or branched-chain alkyl.On the contrary, straight chain and branched-chain alkyl can be by one or more cycloalkyl substituted (promptly can be cycloalkylalkyls, as cyclohexyl methyl etc.).And, unless otherwise prescribed, above alkyl can be by preferential and be independently selected from halogen (for example F, Cl, Br), alkoxyl group (methoxyl group for example, oxyethyl group, propoxy-, butoxy etc.), hydroxyl, amino, and alkyl monosubstituted amino (as methylamino, ethylamino, propyl group amino etc.) and dialkyl amido (dimethylamino for example, diethylamino, dipropyl amino, diisopropylaminoethyl, piperidino-(1-position only) etc.) and the one or more groups in the trialkyl silyl (for example trimethyl silyl, triphenyl silyl etc.) replace.Unless otherwise prescribed, the above definition of term " alkyl " also is applicable to the group that comprises one or more alkyl.
What term used herein " alkenyl " was meant as mentioned definition has one or more pairs of keys and/or a triple-linked " alkyl ".The example of alkenyl is including, but not limited to vinyl, propenyl, allyl group, butenyl, propargyl, 1,4-butadienyl, pseudoallyl, cyclopentenyl, cyclohexenyl, cyclooctene, cyclopentadienyl, cyclohexadienyl, cyclooctadiene base etc.
Term used herein " alkoxyl group " is meant alkyl or alkenyl ether, and wherein term " alkyl " and " alkenyl " are as defined above.The example of the alkylether radicals that is fit to is including, but not limited to methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, allyloxy, trifluoromethoxy etc.
Term used herein " aryl " is meant aromatic group; phenyl for example; naphthyl, camomile cyclic group, phenanthryl or anthryl etc.; they are chosen wantonly and contain one or more (for example 2 or 3) heteroatomss (preferentially being selected from N, O and S and their combination) and/or carry one or more identical or different substituting groups in ring; alkoxyl group for example, aryl, halogen; hydroxyl; amino, alkyl monosubstituted amino, dialkyl amido; nitro; the trialkyl silyl, alkyl-CO, alkyl sulphonyl; alkyl-OCO etc., these terms as defined herein.Illustrate and the example of nonrestrictive aryl is a phenyl, naphthyl, fluorenyl, chloro-phenyl-, dichlorophenyl, fluorophenyl, perfluorophenyl, hydroxy phenyl, anisyl, xenyl, nitrophenyl, acetylphenyl, aminophenyl, pyridyl, pyridazinyl, quinolyl etc.When providing the carbon number of aryl in this article, ring hetero atom is by carbon atom.Unless otherwise prescribed, the above definition of term " aryl " also is applicable to the group that contains one or more aryl.For example, term " aryloxy " is meant that wherein term " aryl " is as the aryl ether of above definition.
Term used herein " alkyl " comprises alkyl, alkenyl, and aralkyl, aromatic yl alkenyl and alkylaryl, term " alkyl " wherein, " alkenyl " and " aryl " are as defined above.Preferred alkyl contains 1-100,000 carbon atom, 1-10,000 carbon atom, 1-1000 carbon atom, 1-500 carbon atom, 1-100 carbon atom, 1-20 carbon atom, 1-10 carbon atom, or 1-6 carbon atom.
Term used herein " halogen " is meant fluorine, chlorine, bromine and iodine or their any subclass.
Activator
Connection metallocene complex of the present invention is activation in every way usually, but has the compound of the empty hapto of coordination, insertion and olefin polymerization with acquisition.For patent specification and appended claims, it is any any compound that can activate above-mentioned catalyst complexes by the neutral catalyst title complex is converted into the catalytic activity catalyst complexes that term " activator " is defined as.The limiting examples of activator comprises aikyiaiurnirsoxan beta, aluminum alkyls and ionization activator, and they can be neutrality or ionic compound.
A, aikyiaiurnirsoxan beta and alkyl aluminum activator
In one embodiment, utilize aikyiaiurnirsoxan beta to activate connection metallocene complex of the present invention.Aikyiaiurnirsoxan beta generally is the compound of oligomeric, ring-type or acyclic containing-Al (R)-O-subunit (general 6-40), and wherein R is an alkyl.Illustrate and the example of nonrestrictive aikyiaiurnirsoxan beta comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.Aikyiaiurnirsoxan beta can prepare by the hydrolysis of each trialkyl aluminium compound.MMAO can prepare by the hydrolysis of trimethyl aluminium and senior trialkyl aluminium compound such as triisobutyl aluminium, they usually in aliphatic solvents solubleness higher and more stable in storage process.Have many kinds to prepare the method for aikyiaiurnirsoxan beta and modified alumoxane, their limiting examples is described in U.S. patent No.4,665,208,4,952,540,5,091,352,5,206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,308,815,5,329,032,5,248,801,5,235,081,5,157,137,5,103,031,5,391,793,5,391,529,5,693,838,5,731,253,5,731,451,5,744,656,5,847,177,5,854,166,5,856,256 and 5,939,346 and European patent publication EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594 218 and EP-B1-0 586 665, and among PCT publication WO 94/10180 and the WO99/15534.Another aikyiaiurnirsoxan beta is 3A type MMAO promotor (from Akzo Chemicals, Inc. is purchased, at U.S. patent No.5, under 041,584 the protection with the trade(brand)name of 3A type modified methylaluminoxane).
Can nonrestrictive example comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium etc. as the example of the alkylaluminium cpd of the activator of connection metallocene complex of the present invention.
B, ionization activator
Also within the scope of the present invention be, use ionization or stoichiometric calculation activator (stoichiometric activator) neutrality or ion, as three normal-butyl ammonium four (pentafluorophenyl group) boron, three perfluorophenyl boron metalloid precursors or three perfluor naphthyl boron metalloid precursors, many halogenations borine negatively charged ion (for example consulting WO 98/43983) of mixing, boric acid (for example consulting U.S. patent No.5,942,459) and their combination.Also within the scope of the present invention be that neutrality or ion activation agent are used separately or be used in combination with aikyiaiurnirsoxan beta or modified alumoxane activator.
The limiting examples of neutral stoichiometric calculation activator comprises that three replace boron, tellurium, aluminium, gallium, indium and their mixture.Three substituting groups can independently be selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxyl group and halogen group separately.Preferably, these three groups independently are selected from halogen, single or many ring (comprising halo) aryl, alkyl, alkoxyl group and alkenyl and their combination.The alkyl that preferably has 1-20 carbon atom has the alkenyl of 1-20 carbon atom, has the alkoxyl group of 1-20 carbon atom and has the aryl (comprising substituted aryl) of 6-20 carbon atom.More preferably, these three groups independently are selected from the alkyl with 1-4 carbon atom, phenyl and naphthyl.Also more preferably, these three groups are halogenations, the preferred fluorinated aryl.Most preferably, neutral stoichiometric calculation activator is three perfluorophenyl boron or three perfluor naphthyl boron.
Ion chemistry calculates activator compound can contain active proton, or associates with the residual ion of this ionizing compound but be not coordinated in or only loosely be coordinated in some other positively charged ions of the residual ion of this ionizing compound.These compounds are described in european publishing thing EP-A-0 570982, and EP-A-0 520 732, and EP-A-0 495 375, and EP-B1-0 500 944, EP-A-0 277003 and EP-A-0 277 004, and U.S. patent Nos.5,153,157,5,198,401,5,066,741,5,206,197,5,241,025,5,384,299,5, in 502,124 and 5,643,847.
In a preferred embodiment, the stoichiometric calculation activator comprises positively charged ion and anionic group, can represent with general formula VI:
(L-H) d +(A D-) general formula VI
Wherein: L is a neutral Lewis base; H is a hydrogen; (L-H) +It is Bronsted acid; A D-Be to have the non-coordination anion of electric charge d-and the integer that d is 1-3.
Cationic components (L-H) d +Can comprise can be protonated or capture the structure division of catalyst precursor compound, as alkyl or aryl, obtains Bronsted acid such as proton or the protonated Lewis base or the reducible Lewis acid of cationic transition metal material.
Activation positively charged ion (L-H) d +It can be Bronsted acid, can give catalyst precursor with proton, obtain transition-metal cation, comprise ammonium, oxygen, phosphorus, silicomethane class and their mixture, preferably by methylamine, aniline, dimethylamine, diethylamine, methylphenylamine, diphenylamine, Trimethylamine 99, triethylamine, N, accelerine, methyldiphenyl base amine, pyridine, right-bromo-N, accelerine and right-nitro-N, accelerine deutero-ammonium class; By triethyl phosphine, triphenylphosphine and diphenylphosphine deutero-are Phosphorus; By ether such as dme, diethyl ether, tetrahydrofuran (THF) and two  alkane deutero-oxygen classes; By thioether, as diethyl thioether and tetramethylene sulfide deutero-sulfonium class; With their mixture.Activation positively charged ion (L-H) d +Can also be to capture structure division such as silver, carbon (carbonium), Zhuo, carbon (carbenium), ferrocene class and their mixture, preferred carbon or ferrocene class.Most preferably (L-H) +It is triphenylcarbenium.
Anionic group A D-Comprise and have general formula (M K+Q n) D-Those, wherein k is the integer of 1-3; N is the integer of 2-6; N-k=d; M is the element that is selected from 13 families of the periodic table of elements, preferred boron or aluminium; Independently be selected from the hydride ion group with Q, bridging or non-bridged dialkyl amido (amido), halogen, alkoxy radical, fragrant oxygen root, alkyl, substituted hydrocarbon radical, brine alkyl replaces brine alkyl and halogen substituted hydrocarbon radical group, described Q has 20 carbon atoms at the most, and prerequisite is that Q to occur be that the situation of halogen is no more than once.Preferably, each Q is the alkyl of fluoridizing with 1-20 carbon atom; More preferably each Q be fluoro aryl and most preferably each Q be five fluoro aryls.The A that is fit to D-The limiting examples of class comprises as at U.S. patent No.5, disclosed two boron compounds in 447,895, and this patent is introduced at this paper comprehensively and is done reference.
Most preferably, ion chemistry calculates activator (L-H) d +(A D-) be four (perfluorophenyl) boric acid N, accelerine or four (perfluorophenyl) boric acid triphenylcarbenium.
In one aspect, use ionization not contain active proton, but the activation method that can form the ionic compound of catalyst precursor compound positively charged ion and Qi Fei coordination anion also is considered, and be described in EP-A-0 426 637, EP-A-0 573 403 and U.S. patent No.5 are in 387,568.
The metal of activator component or metalloid are at 0.3: 1 to 1000: 1 with the mol ratio that supports the metal that is connected the metalloscene catalyst title complex, preferred 20: 1 to 800: 1, and most preferably in 50: 1 to 500: 1 the scope.At activator is the ionization activator as based on those of negatively charged ion four (pentafluorophenyl group) boron the time, the mol ratio of the metal component of the metal of activator component or metalloid and metalloscene catalyst preferably 0.3: 1 to 3: 1.
When using non-carrying metal ocene catalyst system, the metal of activator component or metalloid are to 10 at 0.3: 1 with the mol ratio of the metal that is connected the metalloscene catalyst title complex, 000: 1, preferred 100: 1 to 5000: 1, most preferably in 500: 1 to 2000: 1 the scope.
Solid support material and loading method
Can use one of loading method as known in the art or like that above connection metalloscene catalyst title complex is combined with one or more solid support materials or carrier as described below.In one embodiment, method of the present invention is used the polymerisation catalyst system of supported form, for example is deposited on carrier or the carrier, be incorporated into carrier or carrier, contact with carrier or carrier, be incorporated in carrier or the carrier, absorption or absorption in carrier or carrier or on carrier or carrier.
Term " carrier " or " carrier " can exchange use, are any solid support materials, preferred porous carrier materials, for example talcum, inorganic oxide and butter.Other carrier comprises resinous support material such as polystyrene, functionalized or crosslinked organic carrier, and as polystyrene divinylbenzene, polyolefine or polymerizable compound, zeolite, clay, or any other organic or inorganic solid support material etc., or their mixture.
Preferred carrier is an inorganic oxide, comprises those 2,3,4,5,13 or 14 family metal oxides.Preferred carrier comprises silicon-dioxide, aluminum oxide, silica-alumina, magnesium chloride and their mixture.Other useful carrier comprises magnesium oxide, titanium dioxide, zirconium white, montmorillonite (EP-B1 0 511 665), zeolite etc.Also have, can use the binding substances of these solid support materials, silicon-dioxide-chromium for example, silica-alumina, silica-titania etc.
Preferably, carrier, most preferably inorganic oxide has at 10-700m 2The surface-area of/g, the mean particle size of the pore volume of 0.1-4.0cc/g and 5-500 μ m.More preferably, the surface-area of carrier is 50-500m 2/ g, pore volume are that 0.5-3.5cc/g and mean particle size are 10-200 μ m.Most preferably, the surface-area of carrier is 100-400m 2/ g, pore volume are that 0.8-3.0cc/g and mean particle size are 5-100 μ m.The mean pore size of carrier of the present invention generally is at 10-1000 , preferred 50-500  and most preferably in the scope of 75-350 .
The case description that supports metallocene catalyst system of the present invention is in U.S. patent Nos.4,701,432,4,808,561,4,912,075,4,925,821,4,937,217,5,008,228,5,238,892,5,240,894,5,332,706,5,346,925,5,422,325,5,466,649,5,466,766,5,468,702,5,529,965,5,554,704,5,629,253,5,639,835,5,625,015,5,643,847,5,665,665,5,698,487,5,714,424,5,723,400,5,723,402,5,731,261,5,759,940,5,767,032,5,770,664 and 5,468,702 and PCT publication WO 95/32995, WO95/14044 is among WO96/06187 and the WO97/02297.
In one embodiment, connection metallocene complex of the present invention can be deposited on the identical or different carrier with activator, perhaps activator can non-supported form use, perhaps can be deposited on the carrier different with carrying metal cyclopentadienyl catalyst compound of the present invention, or the arbitrary combination of these methods.
The operation of measuring the total pore volume of porous support is known in the art.The details of one of these operations is discussed at volume 1, among the Experimental Methods in Catalytic Research (test method in the catalyticing research) (Academic Press, 1968) (specifically consulting the 67-96 page or leaf).This preferable process comprises the classical BET device that uses absorbed nitrogen.Other method well known in the art is described in Innes, Total Porosity and Particle Denstity of FluidCatalysts by Liquid Titration (total porosity and the pellet density of the fluid catalyst by the liquid titration determination), Vol.28, No.3 is among the Analytical Chemistry 332-334 (in March, 1956).
In one embodiment, as at U.S. patent Nos.5,317,036 and 5,693,727 and european publishing thing EP-A-0 593 083 described in, connection metallocenes polymerizing catalyst title complex of the present invention preferably uses with liquid form with non-supported form.Can be as in PCT publication WO 97/46599, the polymerizing catalyst of liquid form being added reactor.
In one embodiment, as the U.S. patent application serial numbers 09/113 that proposes June 10 in 1998, described in 216, connection metallocenes polymerizing catalyst title complex of the present invention can with the carboxylate ester of metal, for example ALUMINUM CARBOXYLIC such as list, two and Aluminium Tristearate Micronized sterile, sad, oleic acid and cyclohexyl butyric acid aluminium are used in combination.
Polymerization process
Connection metalloscene catalyst title complex of the invention described above and catalyst system are suitable for any polymerization process under the temperature and pressure of wide region.Temperature can be at-60 ℃ to 280 ℃, in preferred 50 ℃ to the 200 ℃ scope.In one embodiment, polymerization process is carrying out more than 80 ℃ more than 70 ℃ and preferably.Used pressure can be that 1 atmosphere is pressed onto 500 normal atmosphere or higher.
Polymerization process comprises solution, gas phase, slurry phase and high pressure method or their combination.Especially preferred is the gas phase or the slurry phase polymerisation process of one or more alkene (at least a of it is ethene).
In one embodiment, method of the present invention relates to and has 2-30 carbon atom, preferred 2-12 carbon atom and the more preferably solution of one or more olefinic monomers of 2-8 carbon atom, high pressure, slurry or gas phase polymerization process.The present invention especially is very suitable for the polymerization of two or more olefinic monomers in ethene, propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1 and the decylene-1.
Other monomer that can be used for the inventive method comprises ethylenically unsaturated monomer, has the diolefine of 4-18 carbon atom, conjugation or non-conjugated diene, polyene hydrocarbon, vinyl monomer and cycloolefin.Can be used for non-limiting monomer of the present invention and can comprise norbornylene, norbornadiene, iso-butylene, isoprene, vinyl benzo tetramethylene, vinylbenzene, alkyl-substituted styrene, ethylidene norbornene, Dicyclopentadiene (DCPD) and cyclopentenes.
In the most preferred embodiment of method of the present invention, the multipolymer of preparation ethene, wherein have the 4-15 of containing carbon atom, preferred 4-12 carbon atom and most preferably comonomer and ethene polymerization in gas phase process of at least a alpha-olefin of 4-8 carbon atom.
In another embodiment of method of the present invention, comonomer (optional a kind of of them can the be diene) polymerization that ethene or propylene are different with at least two kinds is to form terpolymer.
In one embodiment, the present invention relates to be used for polypropylene or propylene and one or more other monomers polymerization process of (comprise ethene, and/or have other alkene of 4-12 carbon atom), especially gas phase or slurry phase process.Polyacrylic polymer can use as at U.S. patent Nos.5, and 296,434 and 5,278, the special bridging bulky ligand class of metallocenes Catalyst Production described in 264.
Generally, in gas phase polymerization process, use circulation continuously, wherein in part of reactor assembly round-robin, circulating current (being referred to as recycle stream or fluidizing medium in addition) is heated by heat of polymerization in reactor.This heat cooling system by the reactor outside in another part of this round-robin is removed from the recirculation composition.Generally, at the gas fluidized bed process that is used for producing polymkeric substance, contain one or more monomeric air communication and cross fluidized-bed circulation continuously under reaction conditions in the presence of catalyzer.Air-flow is discharged from fluidized-bed, is recycled in the reactor.Simultaneously, polymer product is discharged from reactor, and adds fresh monomer, (for example consults U.S. patent Nos.4,543,399 to replace the polymeric monomer, 4,588,790,5,028,670,5,317,036,5,352,749,5,405,922,5,436,304,5,453,471,5,462,999,5,616,661 and 5,668,228).
Reactor pressure in gas phase process can be at 100psig (690kPa) in 500psig (3448kPa) scope, preferably in 200psig (1379kPa) arrives the scope of 400psig (2759kPa), more preferably in the scope of 350psig (2414kPa), change at 250psig (1724kPa).
Temperature of reactor in the gas phase process can preferred 60 ℃ to 115 ℃, more preferably change in 70 ℃ to 95 ℃ scope in 70 ℃ to 110 ℃ scope and most preferably at 30 ℃ to 120 ℃.
Other contemplated gas phase process of method of the present invention is included in U.S. patent Nos.5, and 627,242,5,665,818 and 5,677,375, and european publishing thing EP-A-0 794200, those described in EP-A-0 802 202 and the EP-B-634 421.
In preferred embodiments, in the present invention reactor of Li Yonging and method of the present invention can produce surpass 500 lbs polymkeric substance/hour (227kg/hr) to 200,000lbs/hr (90,900kg/hr) or more polymkeric substance, preferably surpass 1000lbs/hr (455kg/hr), more preferably surpass 10,000lbs (4540kg/hr) also more preferably surpasses 25,000lbs/hr (11,300kg/hr), more preferably surpass 35 again, 000lbs/hr (15,900kg/hr), further more preferably surpass 50, and 000lbs/hr (22,700kg/hr) and most preferably surpass 65,000lbs/hr (29,000kg/hr) arrive above 100, and 000lbs/hr (45,500kg/hr).
Slurry phase polymerisation process generally uses 1-50 normal atmosphere and even higher pressure and 0-120 ℃ temperature.In slurry polymerization, in the liquid polymeric diluent media, form the suspension of solid particle polymer, in this liquid polymeric diluent media, add ethene and comonomer again with catalyzer, usually also have hydrogen.From reactor discontinuous or the continuous suspension that comprises thinner of discharging, wherein volatile constituent is separated with polymkeric substance, chooses wantonly after distillation to be recycled in the reactor.The liquid diluent that uses in polymerisation medium generally is the paraffinic hydrocarbons with 3-7 carbon atom, the preferred branched paraffinic hydrocarbons.Used medium should be a liquid under polymerizing condition, and is relative inertness.When using propane medium, this method must and be operated more than the pressure in the reaction diluent critical temperature.Preferably, use hexane or Trimethylmethane medium.
Preferred polymeric technology of the present invention is called as the particle form polymerization, or wherein temperature remains on the following slurry process of temperature that polymkeric substance enters solution.These technology are known in the art, and for example at U.S. patent No.3, description are arranged in 248,179.Other slurry process comprise use loop reactor those and utilize those of a plurality of stirred reactors of series, parallel or their combination.The limiting examples of slurry process comprises continuous loop or stirring tank method.Also have, other case description of slurry process is at U.S. patent No.4, in 613,484.
Polymer product of the present invention
Can be used in various products and end-use application with method of the present invention polymkeric substance of producing and the blend that comprises these polymkeric substance.The polymkeric substance of producing with method of the present invention comprises linear low density polyethylene, elastomerics, plastomer, high density polyethylene(HDPE), new LDPE (film grade), polypropylene and polypropylene copolymer.
Polymkeric substance, general vinyl-type polymer has at 0.86g/cc in the 0.97g/cc scope, preferably in 0.88g/cc arrives the 0.965g/cc scope, more preferably in 0.900g/cc arrives the 0.96g/cc scope, also more preferably arrive 0.95g/cc at 0.905g/cc, also further more preferably 0.910g/cc in the 0.940g/cc scope and most preferably be higher than the density of 0.915g/cc to 0.930g/cc.
Melt strength with the polymkeric substance of Catalyst Production of the present invention is higher than 6cN, preferably is higher than 7cN and most preferably 〉=8cN.For present patent application and appended claims, measure melt strength with Instron capillary rheometer and Goettfert Rheotens melt strength measuring apparatus.The polymer melt wire rod of being extruded by the kapillary die head clamps between two reverse rotation wheels of this device.Pulling speed is with 24mm/sec 2Constant acceleration increase, this controls by the Acceleration Programmer (45917 types, the parameter 12 are provided with down).The maximum drawbar pull (by the unit of cN) that obtained before wire rod ruptures or begins to show draw resonance is measured as melt strength.The temperature of rheometer is set in 190 ℃.The kapillary die head has length and the 0.06 " diameter (0.15cm) of 1 inch (2.54cm).Polymer melt is extruded from die head with the speed of 3 inches/min (7.62cm/min).Distance between die head exit and wheel point of contact should be 3.94 inches (100mm).
The polymkeric substance of producing with method of the present invention generally has greater than 1.5 to 15, especially greater than 2 to 10, and more preferably greater than 2.5 to less than 8, the most preferably molecular weight distribution of 3.0-8, i.e. weight-average molecular weight/number-average molecular weight (Mw/Mn).
In one embodiment, polymkeric substance of the present invention has more than or equal to 3, is preferably greater than 3 Mz/Mw.Mz is a Z-average molecular weight.In another embodiment, polymkeric substance of the present invention has the Mz/Mw more than or equal to 3.0 to 4.In still another preferred embodiment, Mz/Mw is in arriving less than 4 scope greater than 3.
Also have, polymkeric substance of the present invention generally has by forming the narrow composition distribution that Tile Width index (CDBI) is weighed.The further details of measuring the CDBI of multipolymer is known to those technician in this area.For example consult the PCT patent application WO93/03903 that published on February 18th, 1993, the document is here introduced for reference in full.
Polymkeric substance of the present invention has in one embodiment generally and is being higher than 50% to 100%, in preferred 99% the scope, preferably in 55% to 85% scope and more preferably 60% to 80%, also more preferably be higher than 60%, also further preferably be higher than 65% CDBI.In another embodiment, this polymkeric substance has and is lower than 50%, more preferably less than 40% with most preferably be lower than 30% CDBI.
Polymkeric substance of the present invention has at 0.01dg/min in one embodiment to 1000dg/min, more preferably 0.01dg/min is to 100dg/min, also more preferably 0.1dg/min to 50dg/min and most preferably 0.1dg/min pass through melt index (MI) or (I that ASTM-D-1238-E measures in the 10dg/min scope 2).
Polymkeric substance of the present invention has 30 in one embodiment to being lower than 200, and more preferably 35 to being lower than 100, most preferably 40 to 95 melt index ratio (I 21/ I 2) (I 21Measure by ASTM-D-1238-F).
Polymkeric substance of the present invention has in preferred embodiments and preferably is higher than 30, more preferably is higher than 35, also more preferably is higher than 40, further also preferably is higher than 50 and most preferably be higher than 65 melt index ratio (I 21/ I 2).
Polymkeric substance of the present invention can with any other polymer blending and/or coextrusion.The limiting examples of other polymkeric substance comprises the linear low density polyethylene of being produced by common Z-N and/or metallocene catalyst method, elastomerics, plastomer, hp-ldpe, high density polyethylene(HDPE), polypropylene etc.
Polymkeric substance of producing with method of the present invention and their blend can be used for such as film, sheet material and fiber extrude with coextrusion and blowing, injection moulding and rotational molding shaping operation.Film comprises by coextrusion or by blowing or cast film that lamination forms, can be used as Food Contact and contact shrinkable film in the application, antiskid film with non-food product, oriented film, sealing film, oriented film, fast food packaging material, the heavy duty sack, the grocery bag, baking and Frozen Food Packaging material, medical package material, the industry wadding, film etc.Fiber comprises the melt-spun that is used to prepare strainer, diaper, medical clothes, geotextile etc. with weaving or nonwoven in form, solvent spinning and the operation of melt jet fiber.Extruded product comprises medical pipe material, electric wire and cable coating, geomembrane and pond lining.Moulded parts comprises the list and the multilayered structure of forms such as bottle, jar, large-scale hollow piece, rigidity food product containers and toy.
When equivalent, concentration or other value or parameter provided as one group of preferred upper limit value and preferred lower limit value, this was interpreted as specifically disclosing all scopes that formed by any a pair of preferred upper limit value and preferred lower limit value, no matter whether disclose this scope separately.And the higher limit and the lower value of any two (or a plurality of) scopes that provide for special parameter are construed as, and also disclose the scope that the higher limit by the lower value of first scope and second scope is combined to form, and vice versa.
Embodiment
In order to understand the present invention better, comprise its representative advantages, following examples are provided.
Unless otherwise prescribed, all are reflected at and carry out in loft drier under the nitrogen or be connected in the Schlenk pipeline.N-Butyl Lithium (2.5M hexane solution) and solvent be from Aldrich, Milwaukee, and WI buys.The 30wt% toluene solution of methylaluminoxane is from Albermarle, Baton Rouge, and LA buys, and press the sample use.Triisobutyl aluminium is from Akzo Nobel, and Houston TX buys, and presses sample and use.Zr (NMe 2) 4By the described method of people such as Jordan (Organometallics 1995,14,5.) prepare, or from Strem Chemicals, Newburyport, MA buys.Hf (NMe 2) 4Buy from Strem Chemicals.ClCH 2CH 2CH 2SiCl 2(CH 3) and chlorination tri-n-butyl tin (n-butyl 3SnCl) from Gelest, Tullytown, PA buys.
Embodiment 1:ClCH 2CH 2CH 2(CH 3) Si (CpH) (CpMe 4Synthesizing H)
The n-Butyl Lithium (2.5M hexane solution) of 64ml is added drop-wise to-35 ℃ tetramethyl-ring pentadiene in the solution in the tetrahydrofuran (THF) (1 liter, 2 liters of flasks).Thermopositive reaction has taken place, and has obtained dense thick white precipitate.ClCH with 30.63g 2CH 2CH 2SiCl 2(CH 3) join in the slurry of tetramethyl-ring pentadiene lithium.In several hours process, slurry has become colourless solution.The cyclopentadiene lithium of 11.5g is joined in this solution restir 2 hours.Remove and desolvate.Add pentane, filter the gained slurry, obtained the lithium chloride of 13.5g.Dry pentane solution has been isolated the ClCH that is the oily quantitative yield of gold 2CH 2CH 2(CH 3) Si (CpH) (CpMe 4H).
Embodiment 2:ClCH 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) Zr (NMe 2) 2Synthetic
ClCH 2CH 2CH 2(CH 3) Si (CpH) (CpMe 4H) (10.0g) with Zr (NMe 2) 4(8.73g) in toluene (200ml), merge.Solution was stirred 15 minutes down at 100 ℃.Remove and desolvate, obtained yellow solid.Pentane is cooled to-35 ℃, and is used for washing solid.Obtained the product of 11.0g. 1H NMR(CD 2Cl 2)：δ0.624(s)，1.72(m)，1.89(s)，1.92(s)，1.98(s)，2.02(2)，2.63(s)，2.66(s)，3.55(t)，5.64(m)，6.49(m)。
Embodiment 3:HInd CH 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) Zr (NMe 2) 2Synthetic
ClCH with 15.2g 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) Zr (NMe 2) 2Merge down at-35 ℃ with the solution of indenyl lithium in tetrahydrofuran (THF) (150ml) of 3.83g.Through 30 minutes this solution is heated to 60 ℃ then.Remove and desolvate, add pentane again.Filter the pentane slurry, remove lithium chloride.The evaporation of pentane solution has obtained red sticky product. 1HNMR (THF-d8): δ 0.671 (overlapping unimodal), 0.705 (overlapping unimodal), 1.3 (m), 1.96-2.06 (overlapping unimodal), 2.72-2.75 (overlapping unimodal), 3.30 (s), 2.07 (s), 5.69 (m), 5.73 (m), 6.28,6.55,6.75,7.12 (m), 7.38 (m).
Embodiment 4:CpZr (Cl) 2Ind CH 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) Zr (NMe 2) 2Synthetic
HInd CH with 2.0g 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) Zr (NMe 2) 2In diethyl ether, be cooled to-35 ℃.The n-Butyl Lithium (2.5M hexane solution) of 1.35ml is added drop-wise in this solution.The trichlorine cyclopentadienyl is closed zirconium (0.93g) join in this solution, the gained slurry is heated to room temperature, restir spends the night.Remove and desolvate, product (1.7g) extracts with pentane. 1H NMR (CD 2Cl 2): δ 0.635 (overlapping unimodal), 1.3 (m), 1.33 (m), 1.8-1.99 (overlapping unimodal), 2.69 (s), 2.96 (m), 3.15 (m), 5.53 (m), 5.67 (m), 6.01 (s), 6.15 (d), 6.47 (m), 6.68 (d), 7.28 (m), 7.63 (m).
Embodiment 5:CpZr (Cl) 2Ind CH 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) ZrCl 2Synthetic
With CpZr (Cl) 2Ind CH 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) Zr (NMe 2) 2Be dissolved in the methylene dichloride.A large amount of excessive trimethylsilyl chloride are joined in this solution restir 30 minutes.Add pentane,, refilter and dry this product (1.3g) under vacuum to be settled out product. 1H NMR(CD 2Cl 2)：δ0.789(s)，0.800(s)，1.33(m)，1.82(s)，1.83(s)，1.95(s)，1.98(s)，2.99(m)，3.19(m)，5.57(m)，5.69(m)，6.15(s)，6.50(d)，6.69(d)，6.93(m)，7.26(m)，7.64(t)。Annotate: residual TMSNMe 2@0.428 (s), 1.694 (s).
Embodiment 6:ClCH 2CH 2CH 2(CH 3) Si ((3,4) PrCpH) 2Synthesizing of (isomer)
ClCH with 38.9g 2CH 2CH 2SiCl 2(CH 3) join in-70 ℃ the solution of n-propyl cyclopentadienyl lithium (46.3g) in tetrahydrofuran (THF).After 1 hour, this slurry is heated to room temperature.After 2 hours, remove and desolvate.Add pentane, the gained slurry is filtered, obtain the lithium chloride of 17g.Dry pentane solution is isolated as the ClCH of the quantitative yield of reddish-brown oil 2CH 2CH 2(CH 3) Si (PrCpH) 2
Embodiment 7:ClCH 2CH 2CH 2(CH 3) Si ((3,4) PrCp) 2Hf (NMe 2) 2Synthesizing of (isomer)
With ClCH 2CH 2CH 2(CH 3) Si (PrCpH) 2(30.0g) with Hf (NMe 2) 4(31.7g) in toluene (200ml), merge.This solution was stirred 3 hours down at 60 ℃.Remove and desolvate, add pentane, remove the brown powder of trace thus.Pentane solution is dry under vacuum, obtained oil (40.87g), further under 70 ℃ and vacuum dry 3 hours again.
Embodiment 8:LiIndCH 2CH 2CH 2(CH 3) Si ((3,4) PrCp) 2Hf (NMe 2) 2Synthesizing of (isomer)
ClCH with 40.87g 2CH 2CH 2(CH 3) Si ((3,4) PrCp) 2Hf (NMe 2) 2Merge down at-35 ℃ in tetrahydrofuran (THF) (150ml) with the indenyl lithium of 8.32g.Through 3 hours this solution is heated to 60 ℃ then.Remove and desolvate, add ether.Filter this ether slurry, remove lithium chloride.The n-Butyl Lithium of filtering solution and 225.5ml (2.5M hexane solution) reaction.With this solution concentration, add pentane, precipitate fuel-displaced.This oil has obtained orange solids with the pentane washing of 400ml.
Embodiment 9:Cl 2Zr[IndCH 2CH 2CH 2(CH 3) Si ((3,4) PrCp) 2HfCl 2] 2Synthetic
LiIndCH with 10g 2CH 2CH 2(CH 3) Si ((3,4) PrCp) 2Hf (NMe 2) 2ZrCl with 1.7g 4In ether, merge down at-35 ℃.This solution is heated to room temperature, and restir spends the night.Remove and desolvate, add pentane.Filter the pentane slurry, the gained pentane solution is dry under vacuum.The gained orange solids is dissolved in the toluene, at room temperature reacts with a large amount of excessive trimethylsilyl chloride again and spend the night.Remove and desolvate, add pentane again, thereby obtained orange slurry, refilter.This orange/yellow solid is dry under vacuum.
Embodiment 10:ClCH 2CH 2CH 2CH 2CpH's is synthetic
Cyclopentadienyl lithium with 11.4g under-70 ℃ joins 1, in the solution of 4-bromine chlorobutane (27.2g).Through a night this solution is heated to room temperature.Remove and desolvate, and add pentane.Filter the pentane slurry, to remove LiBr.Filtrate is dry under vacuum, has obtained golden oil.This oil under vacuum, distill (70 ℃ of jar temperature, distillation temperature 40-50 ℃, 500mmHg).
Embodiment 11:(ClCH 2CH 2CH 2CH 2Cp) 2Hf (NMe 2) 2Synthetic
With ClCH 2CH 2CH 2CH 2CpH (24.0g) and Hf (NMe 2) 4(25.0g) in toluene (200ml), merge.This solution was stirred 1 hour down at 60 ℃.Remove under vacuum and desolvate, obtained oil, this oil was at several days after fixing. 1H NMR(CD 2Cl 2)：δ1.61(m)，1.68(m)，2.41(t)，2.72(s)，3.47(t)，5.78(m)，5.91(m)。
Embodiment 12:(HIndCH 2CH 2CH 2CH 2Cp) 2Hf (NMe 2) 2Synthetic
(ClCH with 7.7g 2CH 2CH 2CH 2Cp) 2Hf (NMe 2) 2Merge in tetrahydrofuran (THF) (150ml) with the indenyl lithium of 3.25g.Through 1 hour solution is heated to 60 ℃ then.Remove and desolvate, add pentane again.Filter this pentane slurry, remove lithium chloride.Evaporation gained pentane solution has obtained the golden oily of 5.68g. 1H NMR(CD 2Cl 2)：δ1.67(m)，2.48(m)，2.73(s)，3.26(s)，3.34(s)，5.78(m)，5.91(m)，6.15(s)，7.11-7.40(m)。
Embodiment 13:(LiIndCH 2CH 2CH 2CH 2Cp) 2Hf (NMe 2) 2Synthetic
(HIndCH with 5.68g 2CH 2CH 2CH 2Cp) 2Hf (NMe 2) 2Merge with the n-Butyl Lithium (2.5M hexane solution) of 5.82ml.Add pentane, refilter the pentane slurry, obtained the yellow powder of 4.90g. 1H NMR(THF-d8)：δ1.67(m)，1.73(m)，2.48(t)，2.78(s)，2.87(t)，5.72(d)，5.79(m)，5.96(m)，6.38(d)，6.42(m)，7.30(m)。
Embodiment 14:(n-bu) 3Sn's (MeInd) is synthetic
1 (3)-methyl indenes (20g) is dissolved in the diethyl ether.Solution is cooled to-35 ℃.The n-Butyl Lithium of Dropwise 5 9.2ml (2.5M hexane solution).Chlorination tri-n-butyl tin (n-butyl with 50.1g 3SnCl) slowly be added drop-wise in the solution of 1-methyl indenyl lithium.Under vacuum, remove diethylether solvent.Add pentane, refilter slurry.Under vacuum, remove pentane, obtained the product (yellow oil) of 58.3g.
Embodiment 15:1-MeIndZrCl 3Synthetic
ZrCl with 32.4g 4Put in the toluene slurry (300ml).(n-bu) of Dropwise 5 8.3g 3Sn (MeInd).Reactant is stirred a whole night.The orange powder of filtration in slurry, with the pentane flushing, dry under vacuum again.
Embodiment 16:(Cl 2Zr (1-MeInd) Ind-1-CH 2CH 2CH 2CH 2Cp) 2HfCl 2Synthesizing of (isomer)
(LiIndCH with 4.9g 2CH 2CH 2CH 2Cp) 2Hf (NMe 2) 21-MeIndZrCl with 4.27g 3In toluene, merge.The gained slurry is stirred a whole night.Filter the toluene slurry with Celite (celite), this solution and excessive TMSCl reaction (several hours, room temperature).Concentrated solution adds pentane, has obtained orange powder.
Embodiment 17: the preparation of catalyst A
CpZr (Cl) with 0.024g 2IndCH 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) ZrCl 2Merge with the methylaluminoxane that supports of 1.0g, obtained the toluene slurry.After 15 minutes, filter slurry, with the toluene flushing, gained is catalyst-loaded dry under vacuum.
Embodiment 18: the preparation of catalyst B
CpZr (Cl) with 0.630g 2IndCH 2CH 2CH 2(CH 3) Si (Cp) (CpMe 4) ZrCl 2Merge with the methylaluminoxane that supports of 42.0g, obtained the toluene slurry.After 30 minutes, filter slurry, with the pentane flushing, gained catalyst-loaded under vacuum dry a whole night.
Embodiment 19: the preparation of catalyzer C
Cl with 2.0g 2Zr[IndCH 2CH 2CH 2(CH 3) Si ((3,4) PrCp) 2HfCl 2] merge with the methylaluminoxane that supports of 100g, obtained the toluene slurry.After 30 minutes, filter slurry, with the pentane flushing, gained catalyst-loaded under vacuum dry a whole night.
Embodiment 20: the preparation of catalyzer D
(Cl with 1.06g 2Zr (1-MeInd) Ind-1-CH 2CH 2CH 2CH 2Cp) 2HfCl 2Merge with the methylaluminoxane that supports of 42g, obtained the toluene slurry.After 30 minutes, filter slurry, with the pentane flushing, gained catalyst-loaded under vacuum dried overnight.
Embodiment 21: use the ethene-hexene polymerization of catalyst A
Be aggregated in 1 liter of Zipperclave autoclave reactor of stainless steel and carry out.This reactor is equipped with the water jacket that is used for heating and cooling.Injection is injected by elevated pressure nitrogen and is carried out (400ml Trimethylmethane, 10ml hexene and 100 μ l triisobutyl aluminiums).Before polymerization, reactor is used nitrogen purging several hours down at 100 ℃.In injection during catalyzer, in keeping temperature of reaction in 85 ℃, need continuous feed ethene according to what keep reactor pressure constant (130psig ethene).At the appointed time, by cooling and emptying pressure and allow the content of reactor be exposed to air to come stopped reaction.The vaporised liquid component, and at N 2Purge dry down poly-(ethene-hexene-1) resin.By GPC gel permeation chromatography weight-average molecular weight (Mw), number-average molecular weight (Mn) and their ratio Mw/Mn.Hexene introduce wt% by 1H NMR data obtain.
Above operation uses the catalyst A of 25mg to carry out.After 40 minutes, termination reaction.Do not find reactor fouling.The fluoropolymer resin of test 1:32.7g (1962g polymkeric substance/g catalyzer. hour); Mw=59,400, Mn=31,800, Mw/Mn=1.86; Hexene wt%=3.7.The fluoropolymer resin (1655g polymkeric substance/g catalyzer hour) of test 2:27.6g; Mw=62,100, Mn=34,200, Mw/Mn=1.81; Hexene wt%=3.8.
Embodiment 22: the ethene-hexene polymerization process that uses catalyst B
Be aggregated in to use in 8 inches fluidized-bed reactors in the gas phase and carry out.Before polymerization, with the prefabricated cot loading of polyethylene in reactor.Purge with drying nitrogen then.Then, catalyzer (dry powdered), vinyl monomer, comonomer (1-hexene), hydrogen and nitrogen are expelled in the reactor continuously, inject described organometallic compound simultaneously continuously, this compound is injected by independent injection port.By the gas composition of online GC monitoring continuously.Be aggregated under 85 ℃ and carry out.When reactor beds weight reaches certain level, by discharge gate discharging polyethylene product.
Embodiment 22A:
Be aggregated under the hydrogen/ethene ratio of 85 ℃, the reactor pressure of the ethylene partial pressure of 220psia, 350psig, hexene/ethylene molar ratio of 0.014 and 0.0013 and carry out.The product that has prepared about 42lbs.The activity of catalyst B is corresponding to 5ppm Hf in product and 2.3ppm Zr.Product have the melt index of 3.8 (gm/10min) and 27 melt flow than and the density of 0.923g/cc.It is 26.6lb/cu.ft. with bulk density that mean particle size is 0.019 inch.
Embodiment 22B:
Polymerizing condition is identical with embodiment 22A, just the hydrogen ratio difference.Hydrogen is not joined in the reactor.According to the hydrogen that produces in reaction, recording hydrogen/ethene ratio is 0.0003.The product that has prepared about 43lbs.Activity of such catalysts is corresponding to 4.5ppm Hf in product and 1.6ppm Zr.Product have the melt index of 0.3 (gm/10min) and 58 melt flow than and the density of 0.918g/cc.It is 29 lb/cu.ft. with bulk density that mean particle size is 0.019 inch.
Embodiment 23: the ethene-hexene polymerization process that utilizes catalyzer D
Be aggregated in to use in the gas phase and comprise that 18 inches (45.7cm) diameters with 16.5 inches (41.9cm) internal diameters, the gas-phase fluidized-bed reactor of No. 60 reactors carry out.The control ethylene concentration is to keep the constant ethylene partial pressure.Use purified nitrogen directly the catalyst-loaded D of solid to be expelled in the fluidized-bed.Reactor is in the total pressure of 300psig (2069kPa), and 85 ℃ temperature of reactor is operation down, and uses the gas superficial velocity of 2.25ft/sec (68.6cm/sec) to obtain the particulate fluidisation.In order to keep the constant temperature of reactor, raise or reduce the temperature of recycle gas continuously, to adapt to any variation of the heat production speed of bringing owing to polymerization.By discharging the part of bed, thereby fluidized-bed is remained on the constant height to equal the speed that granular product forms speed.Embodiment 23 and comparative example's 24 test and product data provide in table 1.
The comparative example 24: utilize Cl 2Zr (1-MeInd) 2(CH 3CH 2CH 2Cp) 2HfCl 2The polymerization of hybrid catalyst system
The preparation that racemize/meso dichloro two (1-methyl indenyl) closes zirconium.(4.67g, 34.3mmol 2.00equiv.) 1, add a ZrCl by part in the light orange solution in the 2-glycol dimethyl ether (80mL) to (1-methyl indenylization) lithium under-35 ℃ 4(4.00g, 17.2mmol, 1.00equiv.).Reactant at first becomes transparent, sap green, becomes muddy then fast, has throw out to form.Mixture heating up to room temperature, is stirred a whole night.After stirring 18 hours, this muddy orange mixture is evaporated in a vacuum, has stayed orange/yellow solid.(3 * 25ml) extractions, the gained mixture filters this solid, has obtained bright yellow solution and pink solid with methylene dichloride.Yellow solution evaporates in a vacuum, has stayed the glassy yellow powder.Output is 7.05g (98%).Isolating product is to use 1The racemize of H NMR proof and 1: 1 mixture of mesoisomer. 1H NMR (CD 2Cl 2): δ 2.36 (s, 6H, Me), 2.42 (s, 6H, Me), 5.76 (d, 2H, C 5Ring-H), 5.94 (d, 2H, C 5Ring-H), 6.10 (d, 2H, C 5Ring-H), 6.36 (d, 2H, C 5Ring-H), 7.28 (m, 8H, C 6Ring-H), 7.45-7.63 (m, 8H, C 6Ring-H).
The preparation that dichloro two (propyl group cyclopentadienyl) closes hafnium.With HfCl 4(30.00g, 93.7mmol 1.00equiv.) join in cold (35 ℃) ethers (400mL) by part, have obtained white suspension.Stirred suspension tout court, and then be cooled to-35 ℃.(21.38g, 187mmol 2.00equiv.) join in this cold suspension by part, have obtained shallow manila paper (manila)-brown mixture with (propyl group cyclopentadienyl) lithium.To room temperature, restir spends the night with mixture heating up.After stirring 17 hours, filter brown mixture, obtained straw yellow solution and brown solid.This solid washs with ether, and the ethereal solution of merging is concentrated to about 100mL in a vacuum.Filter shallow straw yellow crystal by cold concentration solution, filter in a vacuum again.Output 32.69g (75%).Mother liquor is concentrated to about 20mL once more, again by second batch of crystal of filtering separation and dry in a vacuum.Ultimate production is 33.59g (77%). 1H NMR (CD 2Cl 2): δ 0.92 (t, 6H, CH 2CH 2CH 3), 1.56 (m, 4H, CH 2CH 2CH 3), 2.60 (t, 4H, CH 2CH 2CH 3), 6.10 (m, 4H, ring-H), 6.21 (m, 4H, ring-H).
Support the preparation that racemize/meso dichloro two (1-methyl indenyl) closes zirconium.Solution and the 39.00g toluene of 30wt%MAO in toluene of 37.27g is merged, obtained transparent colourless solution.With this solution stirring 15 minutes, add 0.675g racemize/meso dichloro two (1-methyl indenyl) then and close zirconium.This solution deepening at first becomes garnet, brightens into transparent orange then very soon.Reactant was stirred 15 minutes, add 30.00g Davison 948 silicon-dioxide (50 μ, dry down) then, with hand-held spatula the stiff mixture of gained was stirred 10 minutes again at 600 ℃.Orange-yellow mixture dry 20 hours has in a vacuum obtained the orange-yellow free-pouring solid of 42.41g (101%).
Support the preparation that dichloro two (propyl group cyclopentadienyl) closes hafnium.Dichloro two (propyl group cyclopentadienyls) closes hafnium and uses the dichloro two (propyl group cyclopentadienyl) of the 30wt%MAO of 37.37g and 0.747g to close hafnium with the similar fashion of closing zirconium with racemize/meso dichloro two (1-methyl indenyl) to support, obtained the white free-pouring solid of 42.13g (100%) like this.
Support and mix dichloro two (propyl group cyclopentadienyl) and close the preparation that hafnium and racemize/meso dichloro two (1-methyl indenyl) close zirconium.Mix dichloro two (propyl group cyclopentadienyl) close hafnium and racemize/meso dichloro two (1-methyl indenyl) close zirconium with racemize/meso dichloro. the similar fashion that two (1-methyl indenyls) close zirconium is used 0.299g dichloro two (propyl group cyclopentadienyl) to close the 30wt%MAO that hafnium and 0.405g racemize/meso dichloro two (1-methyl indenyl) close zirconium and 37.31g and is supported, and has obtained 42.22g (101%) manila paper look free-flowing solid like this.
Use supports and mixes dichloro two (propyl group cyclopentadienyl) and close the polymerization that hafnium and racemize/meso dichloro two (1-methyl indenyl) close zirconium and carry out according to embodiment 23.Embodiment 23 and comparative example's 24 test and product data provide in table 1.
Table 1
Embodiment number The comparative example 24 Catalyzer D
H 2Concentration, (mol ppm) 34 44
Hydrogen flow (sccm) 0.15 0.00
Comonomer concentration (mol%) 0.95 1.67
C 2Concentration (mol%) 35.0 35.0
Comonomer/C 2Throughput ratio 0.114 0.15
C 2Flow velocity (g/hr) 634 459
H 2/C 2Ratio 1.0 1.3
Comonomer/C 2Ratio 0.027 0.048
Rx pressure (psig) 300 300
Temperature of reactor () 175 175
Average bed heavy (g) 1956 1938
Output (g/hr) 471 278
The residence time (hr) 4.2 7.0
C 2Utilization ratio (gC 2/gC 2Polymkeric substance) 1.35 1.65
Mean flow rate (ft/s) 1.59 1.67
The catalyzer timing (minute) 45.0 30.0
Bulk density 0.3855 0.4183
The product data
Melt index (MI) 1.14 1.74
HLMI 31.3 39.8
The HLMI/MI ratio 27.5 22.9
Density (g/cc) 0.9185 0.9192
Mn 33370 20580
Mw 147200 103900
Mz 567000 128000
Mw/Mn 4.41 5.05
Mz/Mw 3.85 1.23
Melt strength (cN) 8.7 27
Though describe and for example clear the present invention with reference to particular, those ordinarily skilled in the art will appreciate that the present invention itself provides this paper not many other variations of explanation.For this reason, so, should only decide scope of the present invention with reference to appended claims.
All prior art files are introduced for reference with licensed whole authorities of this introducing wherein at this paper all sidedly.In addition, the All Files that this paper quoted comprises that The test procedure introduces for reference with whole authorities that this introducing is allowed at this paper all sidedly.

Claims (5)

1, prepare the method for catalyst complexes, comprising:
(a) allow the cyclopentadiene of X-R-A-X-Cp1 and alkali metal containing or class cyclopentadiene structure react, form X-R-A-Cp2Cp1, wherein X is a halogen, each R is an alkyl, A is that silicon or germanium atom and Cp1 represent first cyclopentadiene or class cyclopentadiene structure, wherein Cp2 represents second cyclopentadiene or class cyclopentadiene structure, and it can be identical or different with Cp1;
(b) allow the X-R-A-Cp2Cp1 that obtains by step (a) with have formula M (NR 2) 4The amination metal reaction, wherein M is that 4 family's metals and R are the alkyl with 1-6 carbon atom, thereby forms the first metallocenes product;
(c) allow the first metallocenes product and the 3rd cyclopentadiene or the reaction of class cyclopentadiene structure basic metal that obtains by step (b), form (Cp2) M (NR of H-Cp3-R-A (Cp1) 2) 2, wherein Cp3 represent can with Cp1 or identical or different the 3rd cyclopentadiene or the class cyclopentadiene structure of Cp2;
(d) (Cp2) M (NR of the H-Cp3-R-A (Cp1) that will obtain by step c) 2) 2Deprotonation forms (Cp2) M (NR of Li-Cp3-R-A (Cp1) 2) 2With
(e) allow (Cp2) M (NR of the Li-Cp3-R-A (Cp1) that obtains by step d) 2) 2With Cp4MCl 3Reaction forms Cp4MCl 2Cp3-R-A (Cp1) is M (NR (Cp2) 2) 2, wherein Cp4 represent can with Cp1 or Cp2 or identical or different Fourth Ring pentadiene or the class cyclopentadiene structure of Cp3.
The process of claim 1 wherein in step e) that 2,2 normal Li-Cp3-R-A (Cp1) are M (NR (Cp2) 2) 2And have formula M Cl 4Metal halide reaction, wherein M is 4 family's metals, thereby forms MCl 2(Cp3-R-A (Cp1) is M (NR (Cp2) 2) 2) 2
3, the method for claim 1, it further comprises makes catalyst complexes contact with inorganic oxide carrier.
4, the method for claim 3, it further comprises in conjunction with alumoxane activator or stoichiometric calculation activator.
5, the method for claim 1, it further comprises in conjunction with the activator that supports.
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